JP2022514577A - Thermoplastic resin composition and its molded product - Google Patents

Thermoplastic resin composition and its molded product Download PDF

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JP2022514577A
JP2022514577A JP2021535152A JP2021535152A JP2022514577A JP 2022514577 A JP2022514577 A JP 2022514577A JP 2021535152 A JP2021535152 A JP 2021535152A JP 2021535152 A JP2021535152 A JP 2021535152A JP 2022514577 A JP2022514577 A JP 2022514577A
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thermoplastic resin
aromatic vinyl
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ダ・ウン・スン
テ・フン・キム
チュン・ホ・パク
ヨン・ヒ・アン
ワンレ・チョ
ホ・フン・キム
ジョンミン・ジャン
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エルジー・ケム・リミテッド
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Abstract

本発明は、熱可塑性樹脂組成物及びその成形品に関し、より詳細には、Ａ－１）平均粒径０．０５～０．１５μｍのアクリレートゴムを含むアクリレート－芳香族ビニル化合物－ビニルシアン化合物グラフト共重合体１０～３０重量％、Ａ－２）平均粒径０．３～０．５μｍのアクリレートゴムを含むアクリレート－芳香族ビニル化合物－ビニルシアン化合物グラフト共重合体２０～４０重量％、Ｂ）芳香族ビニル重合体０～３５重量％、及びＣ）ポリメタクリレート１０～６０重量％からなるベース樹脂１００重量部と；Ｄ）ポリアミド０．５～１０重量部とを含むことを特徴とする熱可塑性樹脂組成物及びその成形品に関する。本発明によれば、従来のＡＳＡ系樹脂と比較して、機械的物性及び加工性などが同等以上に維持されながら、耐候性に優れ、表面粗さの値が低いため感性的に柔らかい感じを与え、表面光沢が均一な低光沢熱可塑性樹脂組成物及びその成形品を提供する効果がある。The present invention relates to a thermoplastic resin composition and a molded product thereof. More specifically, A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft containing an acrylate rubber having an average particle size of 0.05 to 0.15 μm. Copolymer 10-30% by weight, A-2) Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing acrylate rubber with an average particle size of 0.3-0.5 μm 20-40% by weight, B) Thermoplastic characterized by containing 100 parts by weight of a base resin composed of 0 to 35% by weight of an aromatic vinyl polymer and 10 to 60% by weight of polymethacrylate; and D) 0.5 to 10 parts by weight of a polyamide. The present invention relates to a resin composition and a molded product thereof. According to the present invention, as compared with the conventional ASA-based resin, the mechanical properties and processability are maintained at the same level or higher, the weather resistance is excellent, and the surface roughness value is low, so that the feeling is sensuously soft. It has the effect of providing a low-gloss thermoplastic resin composition having a uniform surface gloss and a molded product thereof.

Description

〔関連出願との相互参照〕
本出願は、２０１９年０９月０６日付の韓国特許出願第１０－２０１９－０１１０４１７号及び２０２０年０８月２４日付で再出願された韓国特許出願第１０－２０２０－０１０６１３５号に基づく優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として組み込まれる。 [Cross-reference with related applications]
This application provides the benefit of priority under Korean Patent Application No. 10-2019-0110417 dated September 06, 2019 and Korean Patent Application No. 10-2020-0106135 re-filed on August 24, 2020. All the content claimed and disclosed in the literature of the Korean patent application is incorporated herein by reference.

本発明は、熱可塑性樹脂組成物及びその成形品に関し、より詳細には、従来のＡＳＡ系樹脂と比較して、機械的物性及び加工性などが同等以上に維持されながら、耐候性に優れ、表面粗さの値が低いため感性的に柔らかい感じを与え、表面光沢が均一な低光沢熱可塑性樹脂組成物及びその成形品に関する。 The present invention relates to a thermoplastic resin composition and a molded product thereof. More specifically, the present invention has excellent weather resistance while maintaining mechanical properties and processability equal to or higher than those of a conventional ASA-based resin. The present invention relates to a low-gloss thermoplastic resin composition having a low surface roughness value, which gives a sensually soft feeling and a uniform surface gloss, and a molded product thereof.

アクリレート化合物－スチレン－アクリロニトリル共重合体（以下、「ＡＳＡ樹脂」という）は、耐候性、耐老化性、耐化学性、剛性、耐衝撃性及び加工性をすべて備えており、用途が多様であるため、自動車、雑貨及び建築資材分野などで広範囲に用いられる。 The acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as "ASA resin") has all of weather resistance, aging resistance, chemical resistance, rigidity, impact resistance and processability, and has various uses. Therefore, it is widely used in the fields of automobiles, miscellaneous goods, and building materials.

ところが、外装材分野においてＡＳＡ樹脂の場合、人為的なプラスチックの感じを脱した感性樹脂に対するニーズを満たし得る低光沢ＡＳＡ樹脂に対する開発の必要性が増大している。 However, in the field of exterior materials, in the case of ASA resin, there is an increasing need for development of a low-gloss ASA resin that can meet the needs for a sensitive resin that does not feel like an artificial plastic.

前記低光沢ＡＳＡ樹脂としてナイロンなどの結晶性樹脂を用いて低い光沢を実現したが、低光沢に劣らず外装材において重要な物性である耐候性及び表面の質感の向上には限界があった。 Although low gloss was realized by using a crystalline resin such as nylon as the low gloss ASA resin, there was a limit in improving the weather resistance and the surface texture, which are important physical properties in the exterior material as well as the low gloss.

韓国公開特許第１０-２００９－００９５７６４号公報Korean Published Patent No. 10-2009-095764 Gazette

上記の従来技術の問題点を解決するために、本発明は、従来のＡＳＡ系樹脂と比較して、機械的物性及び加工性などが同等以上に維持されながら、耐候性に優れ、表面粗さの値が低いため感性的に柔らかい感じを与え、表面光沢が均一な低光沢熱可塑性樹脂組成物及びその成形品を提供することを目的とする。 In order to solve the above-mentioned problems of the prior art, the present invention has excellent weather resistance and surface roughness while maintaining mechanical properties and processability equal to or higher than those of the conventional ASA-based resin. It is an object of the present invention to provide a low-gloss thermoplastic resin composition having a uniform surface gloss and a molded product thereof, which gives a sensually soft feeling due to a low value of.

本発明の上記目的及びその他の目的は、以下で説明する本発明によって全て達成することができる。 All of the above objects and other objects of the present invention can be achieved by the present invention described below.

上記の目的を達成するために、本発明は、Ａ－１）平均粒径０．０５～０．１５μｍのアクリレートゴムを含むアクリレート－芳香族ビニル化合物－ビニルシアン化合物グラフト共重合体１０～３０重量％、Ａ－２）平均粒径０．３～０．５μｍのアクリレートゴムを含むアクリレート－芳香族ビニル化合物－ビニルシアン化合物グラフト共重合体２０～４０重量％、Ｂ）芳香族ビニル重合体０～３５重量％、及びＣ）ポリメタクリレート１０～６０重量％からなるベース樹脂１００重量部と；Ｄ）ポリアミド０．５～１０重量部とを含むことを特徴とする熱可塑性樹脂組成物及びその成形品を提供する。 In order to achieve the above object, the present invention relates to A-1) 10 to 30 weights of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle size of 0.05 to 0.15 μm. %, A-2) Acrylate containing acrylate rubber with an average particle size of 0.3 to 0.5 μm-Aromatic vinyl compound-Vinyl cyan compound Graft copolymer 20 to 40% by weight, B) Aromatic vinyl polymer 0 to A thermoplastic resin composition and a molded product thereof, which comprises 100 parts by weight of a base resin consisting of 35% by weight and C) 10 to 60% by weight of a polymethacrylate; and D) 0.5 to 10 parts by weight of a polyamide. I will provide a.

本発明によれば、従来のＡＳＡ系樹脂と比較して、機械的物性及び加工性などが同等以上に維持されながら、耐候性に優れ、表面粗さの値が低いため感性的に柔らかい感じを与え、表面光沢が均一な低光沢熱可塑性樹脂組成物及びその成形品を提供する効果がある。 According to the present invention, as compared with the conventional ASA-based resin, the mechanical properties and processability are maintained at the same level or higher, the weather resistance is excellent, and the surface roughness value is low, so that the feeling is sensuously soft. It has the effect of providing a low-gloss thermoplastic resin composition having a uniform surface gloss and a molded product thereof.

以下、本記載の熱可塑性樹脂組成物及びその成形品を詳細に説明する。 Hereinafter, the thermoplastic resin composition described in the present description and a molded product thereof will be described in detail.

本発明者らは、ＡＳＡ樹脂にポリアミドを添加して無光効果を実現しようとするとき、ＡＳＡ樹脂のモフォロジーを調節し、メチルメタクリレート－スチレン－アクリロニトリル共重合体やポリメチルメタクリレートを必須成分として所定の組成比で含む場合に、従来のＡＳＡ系樹脂と比較して、機械的物性及び加工性などが同等以上に維持されながら、耐候性が向上し、表面粗さの値は低くなるため感性的に柔らかく、表面光沢が均一な低光沢熱可塑性樹脂組成物を得ることができることを確認し、これに基づいてさらに研究に邁進して、本発明を完成するようになった。 When the present inventors try to realize a non-lighting effect by adding a polyamide to an ASA resin, the morphology of the ASA resin is adjusted, and a methyl methacrylate-styrene-acrylonitrile copolymer or a polymethyl methacrylate is defined as an essential component. When it is included in the composition ratio of, the weather resistance is improved and the surface roughness value is low, so that the mechanical properties and processability are maintained at the same level or higher as compared with the conventional ASA resin. It was confirmed that a low-gloss thermoplastic resin composition that was soft and had a uniform surface gloss could be obtained, and based on this, further research was carried out to complete the present invention.

本発明の熱可塑性樹脂組成物は、Ａ－１）平均粒径０．０５～０．１５μｍのアクリレートゴムを含むアクリレート－芳香族ビニル化合物－ビニルシアン化合物グラフト共重合体１０～３０重量％、Ａ－２）平均粒径０．３～０．５μｍのアクリレートゴムを含むアクリレート－芳香族ビニル化合物－ビニルシアン化合物グラフト共重合体２０～４０重量％、Ｂ）芳香族ビニル重合体０～３５重量％、及びＣ）ポリメタクリレート１０～６０重量％からなるベース樹脂１００重量部と；Ｄ）ポリアミド０．５～１０重量部とを含むことを特徴とし、このような場合に、従来のＡＳＡ系樹脂と比較して、機械的物性及び加工性などが同等以上に維持されながらも、耐候性に優れ、光沢が低く、表面光沢が均一で、表面粗さの値が低いため感性的に柔らかい感じを与える熱可塑性樹脂組成物を提供するという利点がある。 The thermoplastic resin composition of the present invention comprises A-1) 10 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle size of 0.05 to 0.15 μm, A. -2) 20-40% by weight of acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing acrylate rubber with an average particle size of 0.3 to 0.5 μm, B) 0 to 35% by weight of aromatic vinyl polymer , And C) 100 parts by weight of the base resin composed of 10 to 60% by weight of the polymethacrylate; and D) 0.5 to 10 parts by weight of the polyamide. In comparison, while the mechanical properties and workability are maintained at the same level or higher, the weather resistance is excellent, the gloss is low, the surface gloss is uniform, and the surface roughness value is low, giving a soft feeling. It has the advantage of providing a thermoplastic resin composition.

以下、本記載の熱可塑性樹脂組成物を構成する各成分を詳細に説明すると、次の通りである。 Hereinafter, each component constituting the thermoplastic resin composition described in the present description will be described in detail as follows.

Ａ－１）アクリレート－芳香族ビニル化合物－ビニルシアン化合物グラフト共重合体
前記Ａ－１）グラフト共重合体のアクリレートゴムは、一例として、平均粒径が０．０５～０．１５μｍであってもよく、好ましくは０．１～０．１５μｍであり、より好ましくは０．１２～０．１５μｍ、さらに好ましくは０．１２～０．１４μｍ、または０．１３～０．１５μｍであり、この範囲内で、最終的に製造される熱可塑性樹脂組成物に優れた耐候性、着色性、衝撃強度、耐化学性及び表面光沢特性を付与することができる。 A-1) Acrylate-Aromatic Vinyl Compound-Vinyl Cyan Compound Graft Copolymer The acrylate rubber of the A-1) graft copolymer is, for example, even if the average particle size is 0.05 to 0.15 μm. It is often, preferably 0.1 to 0.15 μm, more preferably 0.12 to 0.15 μm, still more preferably 0.12 to 0.14 μm, or 0.13 to 0.15 μm, within this range. Therefore, it is possible to impart excellent weather resistance, coloring property, impact strength, chemical resistance and surface gloss property to the finally produced thermoplastic resin composition.

前記アクリレートゴムは、好ましくはコアであってもよい。 The acrylate rubber may preferably be a core.

本記載において、平均粒径は、動的光散乱法（ｄｙｎａｍｉｃ ｌｉｇｈｔ ｓｃａｔｔｅｒｉｎｇ）を用いて測定することができ、詳しくはＮｉｃｏｍｐ３８０装置（製品名、製造社：ＰＳＳ）を用いて測定することができる。 In this description, the average particle size can be measured by using a dynamic light scattering method, and more specifically, by using a Nicommp380 apparatus (product name, manufacturer: PSS).

また、本記載において、平均粒径は、動的光散乱法によって測定される粒度分布における算術平均粒径、具体的には散乱強度平均粒径を意味することができる。 Further, in the present description, the average particle size can mean an arithmetic average particle size in a particle size distribution measured by a dynamic light scattering method, specifically, a scattering intensity average particle size.

前記Ａ－１）グラフト共重合体は、一例として１０～３０重量％、好ましくは１５～２５重量％、より好ましくは１５～２０重量％であり、この範囲内で、耐候性、流動性、引張強度及び衝撃強度に優れるという効果がある。 The A-1) graft copolymer is, for example, 10 to 30% by weight, preferably 15 to 25% by weight, more preferably 15 to 20% by weight, and within this range, weather resistance, fluidity, and tensile strength. It has the effect of being excellent in strength and impact strength.

前記Ａ－１）グラフト共重合体は、一例として、アクリレートゴム４０～６０重量％、芳香族ビニル化合物２５～４５重量％及びビニルシアン化合物１０～２０重量％を含んでなってもよく、この範囲内で、耐候性、流動性、引張強度及び衝撃強度に優れるという効果がある。 As an example, the A-1) graft copolymer may contain 40 to 60% by weight of acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound, in this range. Among them, it has the effect of being excellent in weather resistance, fluidity, tensile strength and impact strength.

好ましい例として、前記Ａ－１）グラフト共重合体は、アクリレートゴム４５～５５重量％、芳香族ビニル化合物３０～５０重量％及びビニルシアン化合物５～２０重量％を含んでなってもよく、この範囲内で、耐候性、流動性、引張強度及び衝撃強度に優れるという効果がある。 As a preferred example, the A-1) graft copolymer may contain 45 to 55% by weight of acrylate rubber, 30 to 50% by weight of an aromatic vinyl compound and 5 to 20% by weight of a vinyl cyan compound. Within the range, it has the effect of being excellent in weather resistance, fluidity, tensile strength and impact strength.

より好ましい例として、前記Ａ－１）グラフト共重合体は、アクリレートゴム４５～５５重量％、芳香族ビニル化合物３０～４０重量％及びビニルシアン化合物１０～２０重量％を含んでなってもよく、この範囲内で、耐候性、流動性、引張強度及び衝撃強度に優れるという効果がある。 As a more preferable example, the A-1) graft copolymer may contain 45 to 55% by weight of acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound and 10 to 20% by weight of a vinyl cyan compound. Within this range, it has the effect of being excellent in weather resistance, fluidity, tensile strength and impact strength.

本記載において、ある化合物を含んでなる重合体とは、その化合物を含んで重合された重合体を意味するもので、重合された重合体内の単位体がその化合物に由来する。 In the present description, the polymer containing a certain compound means a polymer polymerized containing the compound, and the unit in the polymerized polymer is derived from the compound.

前記Ａ－１）グラフト共重合体は、一例として乳化重合で製造されてもよく、この場合に、耐化学性、耐候性、流動性、引張強度及び衝撃強度に優れるという効果がある。 The A-1) graft copolymer may be produced by emulsion polymerization as an example, and in this case, it has an effect of being excellent in chemical resistance, weather resistance, fluidity, tensile strength and impact strength.

前記乳化重合は、本発明の属する技術分野で通常行われる乳化グラフト重合方法による場合、特に制限されない。 The emulsion polymerization is not particularly limited in the case of the emulsion graft polymerization method usually performed in the technical field to which the present invention belongs.

前記アクリレートは、一例として、アルキル基の炭素数が２～８個であるアルキルアクリレートからなる群から選択された１種以上であってもよく、好ましくは、アルキル基の炭素数が４～８個であるアルキルアクリレートであり、より好ましくは、ブチルアクリレート又はエチルヘキシルアクリレートであってもよい。 As an example, the acrylate may be one or more selected from the group consisting of alkyl acrylates having 2 to 8 carbon atoms of an alkyl group, and preferably 4 to 8 carbon atoms of an alkyl group. Alkyl acrylate, more preferably butyl acrylate or ethylhexyl acrylate.

前記芳香族ビニル化合物は、一例として、スチレン、α－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン及びｐ－ｔｅｒｔ－ブチルスチレンからなる群から選択された１種以上であってもよく、好ましくはスチレンである。 As an example, the aromatic vinyl compound may be one or more selected from the group consisting of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, and is preferable. Is styrene.

前記ビニルシアン化合物は、一例として、アクリロニトリル、メタクリロニトリル、エチルアクリロニトリル及びイソプロピルアクリロニトリルからなる群から選択された１種以上であってもよく、好ましくはアクリロニトリルである。 As an example, the vinyl cyanide compound may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, and is preferably acrylonitrile.

Ａ－２）アクリレート－芳香族ビニル化合物－ビニルシアン化合物グラフト共重合体
前記Ａ－２）グラフト共重合体のアクリレートゴムは、一例として、平均粒径が０．３～０．５μｍであってもよく、好ましくは０．３５～０．５μｍであってもよく、より好ましくは０．４～０．５μｍ、さらに好ましくは０．４５～０．５０μｍであり、この範囲内で、耐候性が良好ながらも、流動性、引張強度及び衝撃強度などの機械的強度に優れるという効果がある。 A-2) Acrylate-Aromatic Vinyl Compound-Vinyl Cyan Compound Graft Copolymer The acrylate rubber of the A-2) graft copolymer is, for example, even if the average particle size is 0.3 to 0.5 μm. It may be well, preferably 0.35 to 0.5 μm, more preferably 0.4 to 0.5 μm, still more preferably 0.45 to 0.50 μm, and within this range, the weather resistance is good. However, it has the effect of being excellent in mechanical strength such as fluidity, tensile strength and impact strength.

前記アクリレートゴムは、好ましくはコアであってもよい。 The acrylate rubber may preferably be a core.

前記Ａ－２）グラフト共重合体は、一例として２０～４０重量％、好ましくは２５～３５重量％、より好ましくは３０～３５重量％であり、この範囲内で、耐候性、流動性、引張強度及び衝撃強度に優れるという効果がある。 The A-2) graft copolymer is, for example, 20 to 40% by weight, preferably 25 to 35% by weight, more preferably 30 to 35% by weight, and within this range, weather resistance, fluidity, and tensile strength. It has the effect of being excellent in strength and impact strength.

前記Ａ－２）グラフト共重合体は、一例として、アクリレートゴム４０～６０重量％、芳香族ビニル化合物２５～４５重量％及びビニルシアン化合物１０～２０重量％を含んでなってもよく、この範囲内で、耐候性、流動性、引張強度及び衝撃強度に優れるという効果がある。 The A-2) graft copolymer may contain, for example, 40 to 60% by weight of acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound, in this range. Among them, it has the effect of being excellent in weather resistance, fluidity, tensile strength and impact strength.

好ましい例として、前記Ａ－２）グラフト共重合体は、アクリレートゴム４５～５５重量％、芳香族ビニル化合物３０～４０重量％及びビニルシアン化合物１０～２０重量％を含んでなってもよく、この範囲内で、耐候性、流動性、引張強度及び衝撃強度に優れるという効果がある。 As a preferred example, the A-2) graft copolymer may contain 45 to 55% by weight of acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound and 10 to 20% by weight of a vinyl cyan compound. Within the range, it has the effect of being excellent in weather resistance, fluidity, tensile strength and impact strength.

前記Ａ－１）グラフト共重合体は、好ましくは、前記Ａ－２）グラフト共重合体よりも少ない量で含まれてもよく、より好ましくは、前記Ａ－１）グラフト共重合体と前記Ａ－２）グラフト共重合体との重量比が１：１．１～１：４、より好ましくは１：１．２～１：２であり、この範囲内で、耐候性、流動性、引張強度及び衝撃強度に優れるという効果がある。 The A-1) graft copolymer may be contained in a smaller amount than the A-2) graft copolymer, and more preferably, the A-1) graft copolymer and the A. -2) The weight ratio with the graft copolymer is 1: 1.1 to 1: 4, more preferably 1: 1.2 to 1: 2, and within this range, weather resistance, fluidity, and tensile strength. It also has the effect of being excellent in impact strength.

前記Ａ－１）グラフト共重合体とＡ－２）グラフト共重合体の重量の和は、好ましくは、ベース樹脂に対して４０～６０重量％、より好ましくは４５～５５重量％、さらに好ましくは４７～５３重量％であり、この範囲内で、耐候性、流動性、引張強度及び衝撃強度に優れるという効果がある。 The sum of the weights of the A-1) graft copolymer and the A-2) graft copolymer is preferably 40 to 60% by weight, more preferably 45 to 55% by weight, still more preferably, based on the base resin. It is 47 to 53% by weight, and within this range, it has an effect of being excellent in weather resistance, fluidity, tensile strength and impact strength.

前記Ａ－２）グラフト共重合体は、一例として乳化重合で製造されてもよく、この場合に、耐候性、流動性、引張強度及び衝撃強度に優れるという効果がある。 The A-2) graft copolymer may be produced by emulsion polymerization as an example, and in this case, it has an effect of being excellent in weather resistance, fluidity, tensile strength and impact strength.

前記乳化重合は、本発明の属する技術分野で通常行われる乳化グラフト重合方法による場合、特に制限されない。 The emulsion polymerization is not particularly limited in the case of the emulsion graft polymerization method usually performed in the technical field to which the present invention belongs.

Ｂ）芳香族ビニル重合体
前記Ｂ）芳香族ビニル重合体は、一例として０～３５重量％であってもよく、好ましくは１０～３５重量％であってもよく、より好ましくは１０重量％未満であり、さらに好ましくは５重量％未満であり、含まれないことが最も好ましく、この範囲内で、耐候性に優れ、特に表面粗さの値が大幅に低くなるため、光沢が均一で、手で触れたときに柔らかい感じがするという利点がある。 B) Aromatic vinyl polymer The B) aromatic vinyl polymer may be, for example, 0 to 35% by weight, preferably 10 to 35% by weight, and more preferably less than 10% by weight. It is more preferably less than 5% by weight and most preferably not contained, and within this range, the weather resistance is excellent, and in particular, the surface roughness value is significantly lowered, so that the gloss is uniform and the hand is used. It has the advantage that it feels soft when touched with.

前記Ｂ）芳香族ビニル重合体は、芳香族ビニル化合物６５～８０重量％及びビニルシアン化合物２０～３５重量％を含んでなることが好ましく、この範囲内で、耐化学性及び衝撃強度に優れるという効果がある。 The B) aromatic vinyl polymer preferably contains 65 to 80% by weight of the aromatic vinyl compound and 20 to 35% by weight of the vinyl cyanide compound, and within this range, it is said to be excellent in chemical resistance and impact strength. effective.

前記Ｂ）芳香族ビニル重合体は、一例として、重量平均分子量が８０，０００～１８０，０００ｇ／ｍｏｌであり、好ましくは８０，０００～１６０，０００ｇ／ｍｏｌであり、この範囲内で、引張強度及び衝撃強度などに優れるという効果がある。 As an example, the aromatic vinyl polymer B) has a weight average molecular weight of 80,000 to 180,000 g / mol, preferably 80,000 to 160,000 g / mol, and the tensile strength is within this range. It also has the effect of being excellent in impact strength.

前記Ｂ）芳香族ビニル重合体は、一例として、芳香族ビニル化合物－ビニルシアン化合物共重合体であり、好ましい例として、スチレン－アクリロニトリル共重合体（ＳＡＮ樹脂）、α－メチルスチレン－アクリロニトリル共重合体（耐熱ＳＡＮ樹脂）、またはこれらの混合物であってもよく、この場合に、耐熱度などに優れるという効果がある。 The B) aromatic vinyl polymer is, for example, an aromatic vinyl compound-vinyl cyan compound copolymer, and preferred examples are a styrene-acrylonitrile copolymer (SAN resin) and an α-methylstyrene-acrylonitrile co-weight. It may be a combination (heat-resistant SAN resin) or a mixture thereof, and in this case, it has an effect of being excellent in heat resistance and the like.

前記スチレン－アクリロニトリル共重合体は、好ましくは１５～３５重量％であってもよく、より好ましくは１５～２５重量％であり、この範囲内で、耐熱度などに優れるという効果がある。 The styrene-acrylonitrile copolymer may be preferably 15 to 35% by weight, more preferably 15 to 25% by weight, and within this range, there is an effect of excellent heat resistance and the like.

前記スチレン－アクリロニトリル共重合体は、スチレン６５～８０重量％及びアクリロニトリル２０～３５重量％を含んでなることが好ましく、この範囲内で、加工性及び衝撃強度に優れるという効果がある。 The styrene-acrylonitrile copolymer preferably contains 65 to 80% by weight of styrene and 20 to 35% by weight of acrylonitrile, and within this range, it has an effect of being excellent in processability and impact strength.

前記スチレン－アクリロニトリル共重合体は、一例として、重量平均分子量が１００，０００～１８０，０００ｇ／ｍｏｌであり、好ましくは１００，０００～１５０，０００ｇ／ｍｏｌであり、この範囲内で、耐熱度などに優れるという効果がある。 As an example, the styrene-acrylonitrile copolymer has a weight average molecular weight of 100,000 to 180,000 g / mol, preferably 100,000 to 150,000 g / mol, and within this range, heat resistance and the like. It has the effect of being excellent.

前記α－メチルスチレン－アクリロニトリル共重合体は、好ましくは１０～２０重量％であってもよく、より好ましくは１２～１８重量％であり、この範囲内で、耐熱度などに優れるという効果がある。 The α-methylstyrene-acrylonitrile copolymer may be preferably 10 to 20% by weight, more preferably 12 to 18% by weight, and within this range, there is an effect of excellent heat resistance and the like. ..

前記α－メチルスチレン－アクリロニトリル共重合体は、α－メチルスチレン７０～７５重量％及びアクリロニトリル２５～３０重量％を含んでなることが好ましく、より好ましくは、α－メチルスチレン６０～７５重量％、スチレン０～１０重量％及びアクリロニトリル２０～３０重量％を含んでなるか、又は、α－メチルスチレン６０～７０重量％、スチレン０～１０重量％及びアクリロニトリル２５～３０重量％を含んでなってもよく、さらに好ましくは、α－メチルスチレン６０～７５重量％、スチレン５～１０重量％及びアクリロニトリル２０～３０重量％を含んでなるか、又は、α－メチルスチレン６０～７０重量％、スチレン５～１０重量％及びアクリロニトリル２５～３０重量％を含んでなってもよく、この範囲内で、耐熱度などに優れるという効果がある。 The α-methylstyrene-acrylonitrile copolymer preferably contains 70 to 75% by weight of α-methylstyrene and 25 to 30% by weight of acrylonitrile, and more preferably 60 to 75% by weight of α-methylstyrene. It may contain 0-10% by weight of styrene and 20-30% by weight of acrylonitrile, or 60-70% by weight of α-methylstyrene, 0-10% by weight of styrene and 25-30% by weight of acrylonitrile. Well, more preferably, it comprises 60-75% by weight of α-methylstyrene, 5-10% by weight of styrene and 20-30% by weight of acrylonitrile, or 60-70% by weight of α-methylstyrene, 5-70% by weight of styrene. It may contain 10% by weight and 25 to 30% by weight of acrylonitrile, and within this range, it has an effect of being excellent in heat resistance and the like.

前記α－メチルスチレン－アクリロニトリル共重合体は、重量平均分子量が８０，０００～１２０，０００ｇ／ｍｏｌであることが好ましく、この範囲内で、耐熱度などに優れるという効果がある。 The α-methylstyrene-acrylonitrile copolymer preferably has a weight average molecular weight of 80,000 to 120,000 g / mol, and within this range, it has an effect of being excellent in heat resistance and the like.

本記載において、重量平均分子量は、特に定義しない限り、ＧＰＣ（ゲルパーミエーションクロマトグラフィー（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）、ｗａｔｅｒｓ ｂｒｅｅｚｅ）を用いて測定することができ、具体例として、溶出液としてＴＨＦ（テトラヒドロフラン）を用いて、ＧＰＣ（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ、ｗａｔｅｒｓ ｂｒｅｅｚｅ）を介して、標準ＰＳ（標準ポリスチレン（ｓｔａｎｄａｒｄ ｐｏｌｙｓｔｙｒｅｎｅ））試料に対する相対値として測定することができる。 In the present description, the weight average molecular weight can be measured by using GPC (Gel Permeation Chromatography, waters breath) unless otherwise specified, and as a specific example, THF (tetratetra) as an eluent is used. Can be measured as a relative value to a standard PS (standard polystyrene (standard polystyle)) sample via GPC (Gel Permeation Chromatography, waters breathe).

前記Ｂ）芳香族ビニル重合体は、一例として、懸濁重合、乳化重合、溶液重合または塊状重合により製造されてもよく、この場合に、耐熱性及び流動性などに優れるという効果がある。 The B) aromatic vinyl polymer may be produced, for example, by suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization, and in this case, it has an effect of being excellent in heat resistance and fluidity.

前記懸濁重合、乳化重合、溶液重合及び塊状重合は、それぞれ、本発明の属する技術分野で通常行われる溶液重合及び塊状重合方法による場合、特に制限されない。 The suspension polymerization, emulsion polymerization, solution polymerization and bulk polymerization are not particularly limited as long as they are based on the solution polymerization and bulk polymerization methods usually performed in the technical field to which the present invention belongs, respectively.

Ｃ）ポリメタクリレート
前記Ｃ）ポリメタクリレートは、一例として１０～６０重量％であってもよく、好ましくは２５～５５重量％、より好ましくは２５～５０重量％、さらに好ましくは３０～５０重量％、より一層好ましくは３５～５０重量％、最も好ましくは４５～５０重量％であり、この範囲内で、従来のＡＳＡ系樹脂と比較して、機械的物性及び加工性などが同等以上に維持されながら、耐候性が大きく向上し、表面粗さの値が非常に低いため感性的に柔らかいという利点がある。 C) Polymethacrylate The C) polymethacrylate may be, for example, 10 to 60% by weight, preferably 25 to 55% by weight, more preferably 25 to 50% by weight, still more preferably 30 to 50% by weight. It is even more preferably 35 to 50% by weight, and most preferably 45 to 50% by weight, and within this range, the mechanical properties and processability are maintained at the same level or higher as compared with the conventional ASA resin. The weather resistance is greatly improved, and the surface roughness value is very low, so that there is an advantage that it is sensuously soft.

前記Ｃ）ポリメタクリレートは、好ましくはメタクリレート単量体を５５重量％以上含み、より好ましくは６０重量％以上、最も好ましくは６５重量％以上含み、この範囲内で、耐候性が大きく向上し、表面粗さの値が非常に低いため感性的に柔らかいという効果がある。 The C) polymethacrylate preferably contains 55% by weight or more of a methacrylate monomer, more preferably 60% by weight or more, and most preferably 65% by weight or more, and within this range, the weather resistance is greatly improved and the surface surface is improved. Since the roughness value is very low, it has the effect of being sensuously soft.

前記メタクリレート単量体は、一例として、アルキル基の炭素数が１～１５であるアルキルメタクリレートであってもよく、具体例として、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート、２－エチルブチルメタクリレート、２－エチルヘキシルメタクリレート及びラウリルメタクリレートからなる群から選択された１種以上であってもよく、好ましくは、炭素数１～４個の鎖状アルキル基を含むアルキルメタクリレートであってもよく、より好ましくはメチルメタクリレートであってもよい。 As an example, the methacrylate monomer may be an alkyl methacrylate having 1 to 15 carbon atoms of an alkyl group, and as specific examples, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2-. It may be one or more selected from the group consisting of ethylhexyl methacrylate and lauryl methacrylate, preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, and more preferably a methyl methacrylate. May be.

前記Ｃ）ポリメタクリレートは、好ましくは、ポリメチルメタクリレート樹脂及びメチルメタクリレート－スチレン－アクリロニトリル共重合体からなる群から選択された１種以上であり、より好ましくは、ポリメチルメタクリレート樹脂またはメチルメタクリレート－スチレン－アクリロニトリル共重合体であり、さらに好ましくはポリメチルメタクリレート樹脂であり、この範囲内で、耐候性がさらに優れ、表面粗さの値が低いため感性的に柔らかいという効果がある。 The C) polymethacrylate is preferably one or more selected from the group consisting of the polymethylmethacrylate resin and the methylmethacrylate-styrene-acrylonitrile copolymer, and more preferably the polymethylmethacrylate resin or the methylmethacrylate-styrene. -It is an acrylonitrile copolymer, more preferably a polymethylmethacrylate resin, and within this range, it has an effect of further excellent weather resistance and a low surface roughness value, so that it is sensuously soft.

前記ポリメチルメタクリレート樹脂は、一例として、重量平均分子量が３５，０００～２００，０００ｇ／ｍｏｌであってもよく、好ましくは５０，０００～２００，０００ｇ／ｍｏｌであってもよく、この範囲内で、耐候性がさらに優れ、流動性、引張強度及び衝撃強度に優れ、表面粗さの値が低いため感性的に柔らかいという効果がある。 As an example, the polymethylmethacrylate resin may have a weight average molecular weight of 35,000 to 200,000 g / mol, preferably 50,000 to 200,000 g / mol, within this range. It has further excellent weather resistance, excellent fluidity, tensile strength and impact strength, and has a low surface roughness value, so that it is sensitively soft.

他の例として、ポリメチルメタクリレート樹脂は、重量平均分子量が５０，０００～２００，０００ｇ／ｍｏｌであるポリメチルメタクリレート樹脂（以下、「高分子量ＰＭＭＡ樹脂」という）と、重量平均分子量が３５，０００～４５，０００ｇ／ｍｏｌであるポリメチルメタクリレート樹脂（以下、「低分子量ＰＭＭＡ樹脂」という）との混合物であってもよい。 As another example, the polymethylmethacrylate resin has a weight average molecular weight of 50,000 to 200,000 g / mol and a polymethylmethacrylate resin (hereinafter referred to as “high molecular weight PMMA resin”) and a weight average molecular weight of 35,000. It may be a mixture with a polymethylmethacrylate resin having a molecular weight of up to 45,000 g / mol (hereinafter referred to as “low molecular weight PMMA resin”).

前記高分子量ＰＭＭＡ樹脂と低分子量ＰＭＭＡ樹脂は、一例として、重量比が１：０．１～２．０であってもよく、好ましくは１：１．３～１．７、より好ましくは１：１．４～１．６であってもよく、この範囲内で、流動性、引張強度及び衝撃強度に優れ、耐候性がさらに優れ、表面粗さの値が低いため感性的に柔らかいという効果がある。 As an example, the high molecular weight PMMA resin and the low molecular weight PMMA resin may have a weight ratio of 1: 0.1 to 2.0, preferably 1: 1.3 to 1.7, and more preferably 1: 1. It may be 1.4 to 1.6, and within this range, it has excellent fluidity, tensile strength and impact strength, further excellent weather resistance, and has a low surface roughness value, so that it is sensuously soft. be.

本記載において、ＡとＢの重量比は、Ａ：Ｂの重量比を意味する。 In this description, the weight ratio of A and B means the weight ratio of A: B.

前記メチルメタクリレート－スチレン－アクリロニトリル共重合体は、一例として、メチルメタクリレート６５～８５重量％、スチレン５～３０重量％及びアクリロニトリル５～１０重量％を含んでなり、この範囲内で、耐候性がさらに優れ、表面粗さの値が低いため感性的に柔らかいという効果がある。 The methylmethacrylate-styrene-acrylonitrile copolymer contains, for example, 65 to 85% by weight of methylmethacrylate, 5 to 30% by weight of styrene, and 5 to 10% by weight of acrylonitrile, and within this range, the weather resistance is further increased. It is excellent and has a low surface roughness value, so it has the effect of being sensuously soft.

前記メチルメタクリレート－スチレン－アクリロニトリル共重合体は、一例として、重量平均分子量が７０，０００～１４０，０００ｇ／ｍｏｌであってもよく、他の例として、７０，０００～９０，０００ｇ／ｍｏｌ、または９０，０００ｇ／ｍｏｌ超～１４０，０００ｇ／ｍｏｌ以下であってもよく、この範囲内で、耐候性がさらに優れ、流動性、引張強度及び衝撃強度に優れ、表面粗さの値が低いため感性的に柔らかいという効果がある。 The methylmethacrylate-styrene-acrylonitrile copolymer may have a weight average molecular weight of 70,000 to 140,000 g / mol as an example, and 70,000 to 90,000 g / mol or mol as another example. It may be more than 90,000 g / mol to 140,000 g / mol or less, and within this range, the weather resistance is further excellent, the fluidity, the tensile strength and the impact strength are excellent, and the surface roughness value is low, so that the sensitivity is high. It has the effect of being soft.

他の例として、メチルメタクリレート－スチレン－アクリロニトリル共重合体は、重量平均分子量が７０，０００～９０，０００ｇ／ｍｏｌであるメチルメタクリレート－スチレン－アクリロニトリル共重合体（以下、「低分子量ＳＡＭＭＡ樹脂」という）と、重量平均分子量が１２０，０００～１４０，０００ｇ／ｍｏｌであるメチルメタクリレート－スチレン－アクリロニトリル共重合体（以下、「高分子量ＳＡＭＭＡ樹脂」という）との混合物であってもよい。 As another example, the methylmethacrylate-styrene-acrylonitrile copolymer is a methylmethacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 70,000 to 90,000 g / mol (hereinafter referred to as "low molecular weight SAMMA resin"). ) And a methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 120,000 to 140,000 g / mol (hereinafter referred to as “high molecular weight SAMMA resin”) may be mixed.

前記低分子量ＳＡＭＭＡ樹脂と高分子量ＳＡＭＭＡ樹脂は、一例として、重量比が１：０．１～０．４５であってもよく、好ましくは１：０．２～０．４５であってもよく、より好ましくは１：０．３～０．４５であってもよく、さらに好ましくは１：０．３５～０．４５であってもよく、この範囲内で、耐候性に優れるという利点がある。 As an example, the low molecular weight SAMMA resin and the high molecular weight SAMMA resin may have a weight ratio of 1: 0.1 to 0.45, preferably 1: 0.2 to 0.45. It may be more preferably 1: 0.3 to 0.45, and even more preferably 1: 0.35 to 0.45, and there is an advantage that the weather resistance is excellent within this range.

前記Ｃ）ポリメタクリレートは、一例として、溶液重合、塊状重合、乳化重合または懸濁重合により製造されてもよく、前記溶液重合、塊状重合、乳化重合及び懸濁重合は、それぞれ、本発明の属する技術分野で通常行われる乳化重合及び懸濁重合方法による場合、特に制限されない。 The C) polymethacrylate may be produced, for example, by solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and the solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization, respectively, belong to the present invention. The case of the emulsion polymerization and suspension polymerization methods usually performed in the technical field is not particularly limited.

Ｄ）ポリアミド
前記Ｄ）ポリアミドは、一例として、前記ベース樹脂１００重量部を基準として０．５～１０重量部、好ましくは１～８重量部、より好ましくは４～８重量部、さらに好ましくは４～６重量部であってもよく、この範囲内で、光沢を低下させて無光効果が大きく、物性バランスに優れるという利点がある。 D) Polyamide As an example, the D) polyamide is 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 4 to 8 parts by weight, still more preferably 4 by weight based on 100 parts by weight of the base resin. It may be up to 6 parts by weight, and within this range, there is an advantage that the gloss is lowered, the non-lighting effect is large, and the physical property balance is excellent.

前記Ｄ）ポリアミドは、アミド結合を含む熱可塑性高分子を意味し、具体例として、ポリアミド６、ポリアミド６６（ＰＡ６．６）、ポリアミド４６、ポリアミドｌｌ、ポリアミド１２、ポリアミド６１０、ポリアミド６１２、ポリアミド６／６６、ポリアミド６／６１２、ポリアミドＭＸＤ６、ポリアミド６／ＭＸＤ６、ポリアミド６６／ＭＸＤ６、ポリアミド６Ｔ、ポリアミド６Ｉ、ポリアミド６／６Ｔ、ポリアミド６／６Ｉ、ポリアミド６６／６Ｔ、ポリアミド６６／６Ｉ、ポリアミド６／６Ｔ／６Ｉ、ポリアミド６６／６Ｔ／６Ｉ、ポリアミド９Ｔ、ポリアミド９Ｉ、ポリアミド６／９Ｔ、ポリアミド６／９Ｉ、ポリアミド６６／９Ｔ、ポリアミド６／１２／９Ｔ、ポリアミド６６／１２／９Ｔ、ポリアミド６／１２／９Ｉ及びポリアミド６６／１２／６Ｉからなる群から選択された１種以上であってもよく、好ましくはポリアミド６６（ＰＡ６．６）である。 The D) polyamide means a thermoplastic polymer containing an amide bond, and as specific examples, polyamide 6, polyamide 66 (PA6.6), polyamide 46, polyamide ll, polyamide 12, polyamide 610, polyamide 612, polyamide 6 / 66, Polyamide 6/612, Polyamide MXD6, Polyamide 6 / MXD6, Polyamide 66 / MXD6, Polyamide 6T, Polyamide 6I, Polyamide 6 / 6T, Polyamide 6 / 6I, Polyamide 66 / 6T, Polyamide 66 / 6I, Polyamide 6 / 6T / 6I, Polyamide 66 / 6T / 6I, Polyamide 9T, Polyamide 9I, Polyamide 6 / 9T, Polyamide 6 / 9I, Polyamide 66 / 9T, Polyamide 6/12 / 9T, Polyamide 66/12 / 9T, Polyamide 6/12 It may be one or more selected from the group consisting of / 9I and polyamide 66/12 / 6I, and polyamide 66 (PA6.6) is preferable.

前記Ｄ）ポリアミドは、一例として、融点が２３０℃以上、好ましくは２４０℃以上、より好ましくは２５０℃以上、さらに好ましくは２６０～２７０℃であるものを使用することがよい。 As the D) polyamide, as an example, one having a melting point of 230 ° C. or higher, preferably 240 ° C. or higher, more preferably 250 ° C. or higher, still more preferably 260 to 270 ° C. may be used.

前記Ｄ）ポリアミドは、一例として、相対粘度（硫酸９６％溶液）が２．０～４．０、好ましくは２．０～３．５、より好ましくは２．０～３．０、さらに好ましくは２．４～２．７であるものを使用することがよい。 As an example, the D) polyamide has a relative viscosity (96% sulfuric acid solution) of 2.0 to 4.0, preferably 2.0 to 3.5, more preferably 2.0 to 3.0, and even more preferably. It is preferable to use the one having 2.4 to 2.7.

本記載において、相対粘度は、ＩＳＯ３０７硫酸法により、ウベローデ（Ｕｂｂｅｌｏｈｄｅ）粘度計を用いて測定することができる。 In this description, the relative viscosity can be measured by the ISO307 sulfuric acid method using an Ubbelohde viscometer.

前記Ｄ）ポリアミドの製造方法は、本発明の属する技術分野で通常行われる重合方法であれば、特に制限されず、本発明に係るポリアミドの定義に符合する場合、商業的に購入して用いても構わない。 The method for producing D) polyamide is not particularly limited as long as it is a polymerization method usually performed in the technical field to which the present invention belongs, and if it conforms to the definition of polyamide according to the present invention, it is commercially purchased and used. It doesn't matter.

熱可塑性樹脂組成物
本記載の熱可塑性樹脂組成物は、一例として、オプティカルプロファイラーシステムにより５か所を測定して平均した表面粗さの値が、４以下、好ましくは３．５以下、より好ましくは３以下、さらに好ましくは２．５以下であってもよい。 Thermoplastic resin composition As an example, the thermoplastic resin composition described in this book has a surface roughness value of 4 or less, preferably 3.5 or less, more preferably 3 or less, which is averaged by measuring 5 points by an optical profiler system. May be 3 or less, more preferably 2.5 or less.

前記熱可塑性樹脂組成物は、一例として、ＳＡＥ Ｊ１９６０方法により２０００時間測定した耐候性（△Ｅ）が、４．０以下、好ましくは３．５以下、より好ましくは３．２以下、さらに好ましくは３．０以下であってもよい。 As an example, the thermoplastic resin composition has a weather resistance (ΔE) of 4.0 or less, preferably 3.5 or less, more preferably 3.2 or less, still more preferably 3.2 or less, as measured by the SAE J1960 method for 2000 hours. It may be 3.0 or less.

前記熱可塑性樹脂組成物は、一例として、ＡＳＴＭ Ｄ１２３８に準拠した流動指数（ＭＩ）（２２０℃、荷重１０ｋｇ）が、３ｇ／１０分以上であり、好ましくは７ｇ／１０分以上であり、より好ましくは１０ｇ／１０分以上であり、さらに好ましくは１２ｇ／１０分以上であり、具体例として１２～１５ｇ／１０分であってもよい。 As an example, the thermoplastic resin composition has a flow index (MI) (220 ° C., load of 10 kg) according to ASTM D1238 of 3 g / 10 minutes or more, preferably 7 g / 10 minutes or more, more preferably. Is 10 g / 10 minutes or more, more preferably 12 g / 10 minutes or more, and as a specific example, it may be 12 to 15 g / 10 minutes or more.

前記熱可塑性樹脂組成物は、一例として、ＡＳＴＭ ６３８に準拠した引張強度（１／８インチ）が、２９０ｋｇ／ｃｍ２以上であり、好ましくは３８０ｋｇ／ｃｍ２以上であり、より好ましくは４００ｋｇ／ｃｍ２以上であり、より一層好ましくは４７０ｋｇ／ｃｍ２以上であり、具体例として３８０～４９０ｋｇ／ｃｍ２であってもよい。 As an example, the thermoplastic resin composition has a tensile strength (1/8 inch) according to ASTM 638 of 290 kg / cm 2 or more, preferably 380 kg / cm 2 or more, and more preferably 400 kg / cm. It is 2 or more, more preferably 470 kg / cm 2 or more, and as a specific example, it may be 380 to 490 kg / cm 2 .

前記熱可塑性樹脂組成物は、一例として、ＡＳＴＭ ２５６に準拠したアイゾット衝撃強度（１／４インチ）が、７ｋｇ・ｃｍ／ｃｍ以上であり、好ましくは９ｋｇ・ｃｍ／ｃｍ以上であり、具体例として、７～１１ｋｇ・ｃｍ／ｃｍ又は８～１１ｋｇ・ｃｍ／ｃｍであってもよい。 As an example, the thermoplastic resin composition has an Izod impact strength (1/4 inch) conforming to ASTM 256 of 7 kg · cm / cm or more, preferably 9 kg · cm / cm or more, as a specific example. , 7-11 kg · cm / cm or 8-11 kg · cm / cm.

前記熱可塑性樹脂組成物は、一例として、グロスメーターＶＧ７０００を用いて６０°で測定したフィルム光沢度（ｇｌｏｓｓ）が、１４以下、１１以下または１０．５以下であり、好ましくは９．５以下であり、より好ましくは９．３以下であり、一実施例として、４．８～１４．０又は４．８～１１．０であり、この範囲内で、無光特性に優れながらも物性バランスに優れるという効果がある。したがって、本記載の熱可塑性樹脂組成物は、無光の熱可塑性樹脂組成物とも称することができる。 As an example, the thermoplastic resin composition has a film gloss measured at 60 ° using a gloss meter VG7000, which is 14 or less, 11 or less, or 10.5 or less, preferably 9.5 or less. Yes, more preferably 9.3 or less, and as an example, 4.8 to 14.0 or 4.8 to 11.0, and within this range, the balance of physical properties is excellent while having excellent non-lighting characteristics. It has the effect of being excellent. Therefore, the thermoplastic resin composition described in this invention can also be referred to as a non-light thermoplastic resin composition.

前記熱可塑性樹脂組成物は、必要に応じて選択的に熱安定剤、光安定剤、染料、顔料、着色剤、離型剤、帯電防止剤、抗菌剤、加工助剤、金属不活性化剤、難燃剤、煙抑制剤、滴下防止剤、耐摩擦剤及び耐摩耗剤からなる群から選択された１種以上を、０．０１～５重量部、０．０５～３重量部、０．１～２重量部、または０．５～１重量部さらに含むことができ、この範囲内で、本記載の熱可塑性樹脂組成物本来の物性を低下させないながらも、必要な物性がよく具現されるという効果がある。 The thermoplastic resin composition selectively comprises a heat stabilizer, a light stabilizer, a dye, a pigment, a colorant, a mold release agent, an antistatic agent, an antibacterial agent, a processing aid, and a metal inactivating agent. 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 of one or more selected from the group consisting of flame retardant, smoke suppressant, antistatic agent, friction resistant agent and abrasion resistant agent. It can further contain up to 2 parts by weight or 0.5 to 1 part by weight, and within this range, the necessary physical properties are well realized while not deteriorating the original physical properties of the thermoplastic resin composition described above. effective.

本発明の熱可塑性樹脂組成物の製造方法は、一例として、Ａ－１）平均粒径０．０５～０．１５μｍのアクリレートゴムを含むアクリレート－芳香族ビニル化合物－ビニルシアン化合物グラフト共重合体１０～３０重量％、Ａ－２）平均粒径０．３～０．５μｍのアクリレートゴムを含むアクリレート－芳香族ビニル化合物－ビニルシアン化合物グラフト共重合体２０～４０重量％、Ｂ）芳香族ビニル重合体０～３５重量％、及びＣ）ポリメタクリレート１０～６０重量％からなるベース樹脂１００重量部と；Ｄ）ポリアミド０．５～１０重量部と；を含んで混合した後、２２０～２８０℃の条件下で、押出混練機を用いてペレットを製造するステップを含むことを特徴とし、このような場合に、従来のＡＳＡ系樹脂と比較して、機械的物性及び加工性などが同等以上に維持されながらも耐候性に優れ、光沢が低く、表面光沢が均一で、表面粗さの値が低いため感性的に柔らかい感じを与える熱可塑性樹脂組成物を提供するという利点がある。 As an example, the method for producing a thermoplastic resin composition of the present invention is A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer 10 containing an acrylate rubber having an average particle size of 0.05 to 0.15 μm. ~ 30% by weight, A-2) Acrylic containing acrylate rubber with an average particle size of 0.3 to 0.5 μm-Aromatic vinyl compound-Vinyl cyan compound Graft copolymer 20-40% by weight, B) Aromatic vinyl weight After mixing with 100 parts by weight of the base resin consisting of 0 to 35% by weight of the coalescence and 10 to 60% by weight of the polymethacrylate and D) 0.5 to 10 parts by weight of the polyamide; at 220 to 280 ° C. It is characterized by including a step of producing pellets using an extruder under conditions, and in such a case, the mechanical properties and processability are maintained at the same level or higher as compared with the conventional ASA resin. However, it has an advantage of providing a thermoplastic resin composition which is excellent in weather resistance, has a low gloss, has a uniform surface gloss, and has a low surface roughness value, so that it gives a sensually soft feeling.

前記熱可塑性樹脂組成物の製造方法は、前述した熱可塑性樹脂組成物の全ての技術的特徴を共有する。したがって、重複部分についての説明は省略する。 The method for producing a thermoplastic resin composition shares all the technical features of the above-mentioned thermoplastic resin composition. Therefore, the description of the overlapping portion will be omitted.

前記押出混練機を用いてペレットを製造するステップは、好ましくは２２０～２８０℃下で、より好ましくは２４０～２８０℃下で行うことができ、このとき、温度は、シリンダーに設定された温度を意味する。 The step of producing pellets using the extrusion kneader can be carried out preferably at 220 to 280 ° C., more preferably 240 to 280 ° C., where the temperature is the temperature set in the cylinder. means.

前記押出混練機は、本発明の属する技術分野で通常用いられる押出混練機であれば、特に制限されず、好ましくは二軸押出混練機であってもよい。 The extrusion kneader is not particularly limited as long as it is an extrusion kneader usually used in the technical field to which the present invention belongs, and may be preferably a twin-screw extrusion kneader.

成形品
本記載の成形品は、本記載の熱可塑性樹脂組成物を含むことを特徴とし、この場合に、従来の成形品と比較して、機械的物性及び加工性などが同等以上に維持されながらも耐候性に優れ、光沢が低く、表面光沢が均一で、表面粗さの値が低いため感性的に柔らかい感じを与えるという利点がある。 Molded article The molded article described in this article is characterized by containing the thermoplastic resin composition described in this article, and in this case, the mechanical properties, processability and the like are maintained at the same level or higher as compared with the conventional molded article. However, it has excellent weather resistance, low gloss, uniform surface gloss, and low surface roughness value, so that it has the advantages of giving a soft feeling sensuously.

前記成形品は、一例として、押出成形品又は射出成形品であってもよく、好ましくは建築外装材であり、より好ましくはサイディング（ｓｉｄｉｎｇ）、スライディングドアまたは建具であってもよい。 As an example, the molded product may be an extruded product or an injection molded product, preferably a building exterior material, and more preferably a siding, a sliding door, or a fitting.

前記成形品は、好ましくは、本記載の熱可塑性樹脂組成物を成形温度１９０～２５０℃下で押出又は射出するステップを含んで製造されてもよく、この範囲内で、優れた無光効果が発現されるという利点がある。 The molded product may preferably be manufactured by including a step of extruding or injecting the thermoplastic resin composition described in the present invention at a molding temperature of 190 to 250 ° C., and within this range, an excellent non-lighting effect can be obtained. It has the advantage of being expressed.

本記載の熱可塑性樹脂組成物、その製造方法及び成形品を説明するにおいて、明示的に記載していない他の条件や装備などは、当業界で通常行われる範囲内で適宜選択することができ、特に制限されないことを明示する。 In the description of the thermoplastic resin composition described above, the method for producing the same, and the molded product, other conditions and equipment not explicitly described can be appropriately selected within the range normally used in the art. , Clarify that there are no particular restrictions.

以下、本発明の理解を助けるために好ましい実施例を提示するが、以下の実施例は、本発明を例示するものに過ぎず、本発明の範疇及び技術思想の範囲内で様々な変更及び修正が可能であることは当業者にとって明らかであり、このような変更及び修正が添付の特許請求の範囲に属することも当然である。 Hereinafter, preferred embodiments will be presented to aid understanding of the present invention, but the following examples merely illustrate the present invention, and various changes and modifications are made within the scope of the present invention and technical ideas. It is clear to those skilled in the art that such changes and amendments fall within the scope of the appended claims.

［実施例］
下記の実施例１～１０及び比較例１～３で用いられた物質は、次の通りである。 [Example]
The substances used in Examples 1 to 10 and Comparative Examples 1 to 3 below are as follows.

Ａ－１）乳化重合方式の第１グラフト共重合体（平均粒径１００ｎｍのブチルアクリレート重合体５０重量％、シェル：スチレン３６重量％、アクリロニトリル１４重量％）
Ａ－２）乳化重合方式の第２グラフト共重合体（平均粒径４００ｎｍのブチルアクリレート重合体５０重量％、シェル：スチレン３８重量％、アクリロニトリル１２重量％）
Ｂ－１）バルク重合方式のＳＡＮ樹脂（９２ＲＦ）、
Ｂ－２）バルク重合方式の耐熱ＳＡＮ樹脂（２００ＵＨ）、
Ｃ－１）バルク重合方式のＳＡＭＭＡ樹脂（ＸＴ５００）、
Ｃ－２）バルク重合方式のＳＡＭＭＡ樹脂（ＸＴ５１０）、
Ｃ－３）ＰＭＭＡ樹脂（ＩＨ８３０），
Ｃ－４）ＰＭＭＡ樹脂（ＢＡ６１１）
Ｄ）ＰＡ６．６ A-1) Emulsion polymerization type first graft copolymer (50% by weight of butyl acrylate polymer having an average particle size of 100 nm, shell: 36% by weight of styrene, 14% by weight of acrylonitrile)
A-2) Emulsion polymerization type second graft copolymer (50% by weight of butyl acrylate polymer having an average particle size of 400 nm, shell: 38% by weight of styrene, 12% by weight of acrylonitrile)
B-1) Bulk polymerization method SAN resin (92RF),
B-2) Bulk polymerization type heat resistant SAN resin (200UH),
C-1) Bulk polymerization method SAMMA resin (XT500),
C-2) Bulk polymerization method SAMMA resin (XT510),
C-3) PMMA resin (IH830),
C-4) PMMA resin (BA611)
D) PA6.6

実施例１～１０及び比較例１～３
それぞれ、下記表１に記載された成分及び含量を、二軸押出機にて２８０℃下で混練及び押出してペレットを製造した。製造されたペレットを用いて溶融指数を測定した。また、製造されたペレットを用いて成形温度２２０℃で０．１５Ｔのシートを製造し、フィルムの光沢（ｇｌｏｓｓ）及び表面粗さの値を測定した。さらに、前記製造されたペレットを成形温度２２０℃で射出して物性測定用試片を作製し、これを用いて引張強度及び衝撃強度を測定した。 Examples 1 to 10 and Comparative Examples 1 to 3
The components and contents listed in Table 1 below were kneaded and extruded at 280 ° C. using a twin-screw extruder to produce pellets. The melt index was measured using the manufactured pellets. Further, a 0.15 T sheet was manufactured at a molding temperature of 220 ° C. using the manufactured pellets, and the values of gloss and surface roughness of the film were measured. Further, the manufactured pellets were injected at a molding temperature of 220 ° C. to prepare a sample for measuring physical properties, and the tensile strength and impact strength were measured using the sample.

［試験例］
前記実施例１～１０及び比較例１～３で製造されたペレット、シート及び試片の特性を、下記の方法で測定し、その結果を下記の表１に示した。 [Test example]
The characteristics of the pellets, sheets and specimens produced in Examples 1 to 10 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 1 below.

＊溶融指数（ｍｅｌｔ ｉｎｄｅｘ；ＭＩ）：製造されたペレットを、２２０℃／１０ｋｇの条件下でＡＳＴＭ Ｄ１２３８方法により測定した。 * Melt index (MI): The pellets produced were measured by the ASTM D1238 method under conditions of 220 ° C./10 kg.

＊引張強度（ｋｇ／ｃｍ２）：ＡＳＴＭ ６３８方法により測定した。 * Tensile strength (kg / cm 2 ): Measured by the ASTM 638 method.

＊アイゾット衝撃強度（ｋｇ．ｃｍ／ｃｍ）：ＡＳＴＭ ２５６方法により測定した。 * Izod impact strength (kg. cm / cm): Measured by the ASTM 256 method.

＊フィルム光沢（ｇｌｏｓｓ）：グロスメーター（ｇｌｏｓｓ ｍｅｔｅｒ）ＶＧ７０００を用いて６０°で測定した。 * Film gloss: Measured at 60 ° using a gloss meter VG7000.

＊表面粗さの値：オプティカルプロファイラーシステム（Ｏｐｔｉｃａｌ ｐｒｏｆｉｌｅｒ ｓｙｓｔｅｍ）（ＮＶ－２７００、（株）ナノシステム）により、対物レンズ（Ｏｂｊｅｃｔｉｖｅ ｌｅｎｓ）：１０倍×接眼レンズ１倍（Ｆ．Ｏ．Ｖ：６２８μｍ×４７１μｍ）、モード：ＷＳＩ 枠（Ｅｎｖｅｌｏｐｅ）及びスキャン範囲（Ｓｃａｎ ｒａｎｇｅ）：±３０μｍの条件下で５か所を測定して平均を出した。表面粗さの値が低いと、手で触れたときに柔らかい感じがし、光沢が均一である。 * Surface roughness value: Objective lens: 10x x eyepiece 1x (FOV: 628μm) by Optical profiler system (NV-2700, Nanosystem Co., Ltd.) × 471 μm), mode: WSI frame (Envelope) and scan range (Scan range): 5 points were measured under the condition of ± 30 μm and averaged. When the surface roughness value is low, it feels soft to the touch and the gloss is uniform.

＊耐候性：ＳＡＥ Ｊ１９６０方法により２０００時間測定した後、下記の数式１で計算される△Ｅにより評価した。△Ｅの値が低いと、耐候性に優れる。 * Weather resistance: After measuring for 2000 hours by the SAE J1960 method, it was evaluated by ΔE calculated by the following formula 1. When the value of ΔE is low, the weather resistance is excellent.

Figure 2022514577000001
Figure 2022514577000001

Figure 2022514577000002
Figure 2022514577000002

前記表１に示されたように、本発明に係る熱可塑性樹脂組成物（実施例１～１０参照）は、ポリメタクリレート樹脂を含まない比較例１及び２と比較して、流動指数、引張強度及び衝撃強度などの機械的物性は同等又はそれ以上を維持しながらも耐候性に優れ、表面粗さの値が低いため感性的に柔らかい感じを与え、表面光沢が均一でかつ低いことが確認できた。特に、前記表１を参照すると、ポリメタクリレート樹脂を４０～６０重量％、より具体的には４５～５５重量％の範囲で含む実施例１～３及び実施例７～９の場合、表面粗さの値が３．０以下、具体的には２．０～３．０であり、耐候性（△Ｅ）は３．１以下、具体的には１．３～３．３で、比較例１及び２と比較していずれも非常に優れるため、高い品質の感性樹脂が製造されることが確認できた。 As shown in Table 1, the thermoplastic resin compositions according to the present invention (see Examples 1 to 10) have a flow index and tensile strength as compared with Comparative Examples 1 and 2 containing no polymethacrylate resin. It can be confirmed that the mechanical properties such as impact strength are the same or higher, but the weather resistance is excellent, the surface roughness value is low, so that the surface roughness is sensuously soft, and the surface gloss is uniform and low. rice field. In particular, referring to Table 1, the surface roughness of Examples 1 to 3 and Examples 7 to 9 containing the polymethacrylate resin in the range of 40 to 60% by weight, more specifically 45 to 55% by weight. The value of is 3.0 or less, specifically 2.0 to 3.0, and the weather resistance (ΔE) is 3.1 or less, specifically 1.3 to 3.3, and Comparative Example 1 It was confirmed that high quality sensitive resin was produced because both of them were very excellent as compared with 2 and 2.

一方、ポリアミドを含まない比較例３の場合、光沢（ｇｌｏｓｓ）が６７として、実施例１～９の光沢（ｇｌｏｓｓ）と比較して、少なくは６倍から多くは１４倍と高いため、無光特性を実現して高品質の感性樹脂を製造しようとする本発明の目的とは全く合わないことが確認できた。 On the other hand, in the case of Comparative Example 3 containing no polyamide, the gloss is 67, which is as high as 6 times to 14 times as high as the gloss of Examples 1 to 9, so that there is no light. It was confirmed that the object of the present invention, which aims to realize the characteristics and produce a high-quality sensitive resin, does not meet at all.

Claims (16)

Ａ－１）平均粒径０．０５～０．１５μｍのアクリレートゴムを含むアクリレート－芳香族ビニル化合物－ビニルシアン化合物グラフト共重合体１０～３０重量％、Ａ－２）平均粒径０．３～０．５μｍのアクリレートゴムを含むアクリレート－芳香族ビニル化合物－ビニルシアン化合物グラフト共重合体２０～４０重量％、
Ｂ）芳香族ビニル重合体０～３５重量％、及び
Ｃ）ポリメタクリレート１０～６０重量％からなるベース樹脂１００重量部と；
Ｄ）ポリアミド０．５～１０重量部とを含むことを特徴とする、熱可塑性樹脂組成物。 A-1) Acrylate containing acrylate rubber with an average particle size of 0.05 to 0.15 μm-Aromatic vinyl compound-Vinyl cyan compound Graft copolymer 10 to 30% by weight, A-2) Average particle size 0.3 to Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing 0.5 μm acrylate rubber 20-40% by weight,
B) With 100 parts by weight of the base resin composed of 0 to 35% by weight of the aromatic vinyl polymer and C) 10 to 60% by weight of the polymethacrylate;
D) A thermoplastic resin composition comprising 0.5 to 10 parts by weight of a polyamide. 前記熱可塑性樹脂組成物は、グロスメーターＶＧ７０００を用いて６０°で測定したフィルム光沢度（ｇｌｏｓｓ）が１４以下である無光特性を有することを特徴とする、請求項１に記載の熱可塑性樹脂組成物。 The thermoplastic resin according to claim 1, wherein the thermoplastic resin composition has a non-light property having a film gloss (gloss) of 14 or less measured at 60 ° using a gloss meter VG7000. Composition. 前記熱可塑性樹脂組成物は、オプティカルプロファイラーシステムにより５か所を測定して平均した表面粗さが４以下であることを特徴とする、請求項１又は２に記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin composition has a surface roughness of 4 or less measured at 5 points by an optical profiler system. 前記熱可塑性樹脂組成物は、ＳＡＥ Ｊ１９６０方法により測定した耐候性（△Ｅ）が４．０以下であることを特徴とする、請求項１～３のいずれか一項に記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin composition has a weather resistance (ΔE) of 4.0 or less measured by the SAE J1960 method. thing. 前記Ａ－１）グラフト共重合体は、アクリレートゴム４０～６０重量％、芳香族ビニル化合物２５～４５重量％及びビニルシアン化合物１０～２０重量％を含んでなることを特徴とする、請求項１～４のいずれか一項に記載の熱可塑性樹脂組成物。 A-1) The graft copolymer is characterized by containing 40 to 60% by weight of an acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound. The thermoplastic resin composition according to any one of 4 to 4. 前記Ａ－２）グラフト共重合体は、アクリレートゴム４０～６０重量％、芳香族ビニル化合物２５～４５重量％及びビニルシアン化合物１０～２０重量％を含んでなることを特徴とする、請求項１～５のいずれか一項に記載の熱可塑性樹脂組成物。 A-2) The graft copolymer is characterized by containing 40 to 60% by weight of an acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound. The thermoplastic resin composition according to any one of 5 to 5. 前記Ａ－１）グラフト共重合体は、前記Ａ－２）グラフト共重合体よりも少ない量で含まれることを特徴とする、請求項１～６のいずれか一項に記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to any one of claims 1 to 6, wherein the A-1) graft copolymer is contained in a smaller amount than the A-2) graft copolymer. thing. 前記Ａ－１）グラフト共重合体とＡ－２）グラフト共重合体の重量の和は、ベース樹脂に対して４０～６０重量％であることを特徴とする、請求項１～７のいずれか一項に記載の熱可塑性樹脂組成物。 Any of claims 1 to 7, wherein the sum of the weights of the A-1) graft copolymer and the A-2) graft copolymer is 40 to 60% by weight with respect to the base resin. The thermoplastic resin composition according to item 1. 前記Ｂ）芳香族ビニル重合体は、ベース樹脂に対して１０～３５重量％であることを特徴とする、請求項１～８のいずれか一項に記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to any one of claims 1 to 8, wherein the B) aromatic vinyl polymer is 10 to 35% by weight based on the base resin. 前記Ｂ）芳香族ビニル重合体は、ベース樹脂に対して１０重量％未満であるか、または含まれないことを特徴とする、請求項１～８のいずれか一項に記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to any one of claims 1 to 8, wherein the B) aromatic vinyl polymer is less than 10% by weight or not contained in the base resin. thing. 前記Ｂ）芳香族ビニル重合体は、芳香族ビニル化合物－ビニルシアン化合物共重合体であることを特徴とする、請求項１～１０のいずれか一項に記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to any one of claims 1 to 10, wherein the B) aromatic vinyl polymer is an aromatic vinyl compound-vinyl cyan compound copolymer. 前記Ｃ）ポリメタクリレート樹脂は、メタクリレート単量体を５５重量％以上含んでなることを特徴とする、請求項１～１１のいずれか一項に記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to any one of claims 1 to 11, wherein the C) polymethacrylate resin contains 55% by weight or more of a methacrylate monomer. 前記Ｃ）ポリメタクリレート樹脂は、ポリメチルメタクリレート樹脂、及びメチルメタクリレート－スチレン－アクリロニトリル共重合体からなる群から選択された１種以上であることを特徴とする、請求項１２に記載の熱可塑性樹脂組成物。 The thermoplastic resin according to claim 12, wherein the C) polymethacrylate resin is at least one selected from the group consisting of a polymethylmethacrylate resin and a methylmethacrylate-styrene-acrylonitrile copolymer. Composition. 前記メチルメタクリレート－スチレン－アクリロニトリル共重合体は、メチルメタクリレート６５～８５重量％、スチレン５～３０重量％及びアクリロニトリル５～１０重量％を含んでなることを特徴とする、請求項１３に記載の熱可塑性樹脂組成物。 13. The heat of claim 13, wherein the methylmethacrylate-styrene-acrylonitrile copolymer comprises 65-85% by weight of methylmethacrylate, 5-30% by weight of styrene and 5-10% by weight of acrylonitrile. Plastic resin composition. 前記Ｄ）ポリアミドはポリアミド６．６であることを特徴とする、請求項１～１４のいずれか一項に記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to any one of claims 1 to 14, wherein the D) polyamide is polyamide 6.6. 請求項１～１５のいずれか一項に記載の熱可塑性樹脂組成物を含むことを特徴とする、成形品。 A molded product comprising the thermoplastic resin composition according to any one of claims 1 to 15.
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